Detergent and method of making same



April 2, A1940. E. E. DREGER Er AL f 2,195,512

DETERGENT AND METHOD OF MAKING SAME Filed Nov. 5, 1937 4 Sheets-Sheet l u ww April 2, 1940. E. E. DREGER r-:r AL

DETERGN' AND METHOD 0F MAKING SAME Filed Nov. 5, 1937 4 Sheets-Sheet 2 (Zurf/c Som 7mm M/xf? /Val Mig/$5 76 la ff 37 gis] Summa;

PIF 2 1940 E. E. DRL-:GER ET AL 2,195,512

DETERGENT AND METHOD 0F MAKING SAME Filed Nov. 5, 1937 4 Sheets-'Sheet 3 April 2 w40 E. E. DREGER er' AL n Y 2,195,512

DETERGENT AND METHOD 0F MAKING SAME Filed Nov. 5, 1937 4 Sheets-Sheet 4 gmc/www Patented Apr. 2, i946 OFFECE DETERGIEN'END METHOD 0F WING Emil E. Droger, Summit, N. 3., and John BOB. New York, N. Y., assignors to Comte-Palm olive-Peet Company, Jersey ity, BL'J.. a oorporation of Delaware This invention relates to an improved process for preparing certain chemical compositions especially useful as wetting agents, detergents,

` foaming agents, emulsifying agents, and the like. More particularly, the invention concerns a simple process for preparing a concentrated neutralized vorganic sulphonate produced by reacting a polyhydric alcohol, a sulphonating agent, an aromatic material and a fatty oil or lo fatty acid, which process may conveniently be operated continuously. This process makes it possible to manufacture chemical compositions with excellent wetting, deterging, emulsifying, penetrating, dispersing and lathering properties l5 at a very low cost. Y

In U. S. Patent 2,0l4,502, granted Sept. 17, 1935 to Karl Marx, Karl Brodersen and Matthias Quaedvlieg, a process is described which essentially consists in reacting with a condensing and sulphonating agent a mixture of an aromatic hydrocarbon of the benzene or naphthalene series` and a mono ester ora polyhydricalcohol with a higher fatty acid, the alkali salts of which have soap characteristics, said ester having at least one free hydroxyl group. e

According to the present invention, compositions similar to those described in the Marx et al. patent may be manufactured by an economical process which is, relatively simple in operation 3o and readily adaptable to a continuous procedure'. By the present process, one is able to prepare a A purer type product because of the controlled reaction conditions. For example, the temperature of the reaction may be relatively low, preferably between normal room temperature and 80 lil., whereas prior processes of this type are usually conducted at much higher temperatures. Furthermore, a fatty oil may be used directly as one of the reactants, thus saving considerable time and eifort over those processes which require the separation of the fatty acid from the lfatty oil and the preparation of the monoglvc-A erldes thereof, which steps tend to cause serious discoloration of the fatty acid compound.

A novelproceduref for neutralization of the complex reaction product' prevents any detrimental etfects of tliejalkalion the sulphonated reaction product butstill permits the use of concentrated solutionsof bothv the reaction product 5o and alkali, thus obtaining concentrated solutions of the neutralized material without the numerous l process steps. Heretofore, it has been necessary to use dilute solutions of both the reaction product and the alkali land thento concentrate the g5 resulting dilute solution of the neutralized prod uct, this latter step almost invariably impa the general appearance and effectiveness of the detergent product.

Uniform products and high yields are obtained.

by careful control of the sulphonating agent so 5 that the concentration of the acid at the close of the reaction is relatively high. When the acid is within the preferred range of concentration at the close of the reaction the variable factors of original concentration, strength of acid and the 10 amount of water present and generated in the reaction, do not prevent the completion Aof the reaction and the nal products have good color l and odor and are relatively uniform in composition. 16

In its preferred form, the new process comprises the steps of continuously mixing a sulphonating agent and a polyhydric alcohol; adding to this mixture continuously and with agita-- tion, fatty oil and aromatic material, and after 20 completion of the reaction'-, continuously neutralizing the product by bringing it into conuence with a relatively concentrated solution' of a neutraliizng agent, with agitation, and in the presence of a relatively large body of already 25 neutralized reaction product so as to have conditions of substantial neutrality during this stepA By this process, using but two small mixers, and a neutralizer, which is also small as compared with the equipment ordinarily used for 30 making soap or other detergentmaterials, the, raw materials may be supplied to one end of the apparatus and the finished product withdrawn from the other without any interruption to the continuous i'iow. 35

The proportions of material to be used in the new process may be varied somewhat within the scope of this invention, but it has, been found preferable to use such proportion of fatty oil or.

fatty acid and polyhydric alcohol as wi1l,-when :'40

reacted, yield mono esters and leave a small excess of polyhydric alcohol. Thus when a fatty" oil and glycerine are used, it is preferableto use one molecular proportion of the fatty oil; two molecular proportions plus around 5 per cent of '45 substantially anhydrous glycerine. If a fatty acid is substituted for a fatty oil, it is preferable to use vone molecular proportion of fatty acid to one molecular proportion of anhydrous glycerine, plus an excess of 3 or 4 per cent. Approximately 50 onermolecular weight of the aromatic material will ordinarily be used for each molecular weight of the finished product that is to be made. Enough of the sulphonating agent should be used and the concentration adjusted to be such that the nal product will be completely monoconcentration and quantity that the sulphuric l acid which remains after the reaction has been completed is of a concentration of around 99 per cent, the reaction will be substantially complete. Ii the concentration of the sulphuric acid at the end of the reaction is appreciably less than this, the reaction Will not be complete and the reaction time relatively long. If appreciably greater than 99%, then undesirable by-products will be formed and the product'will be poorer in color and odor. If a poly-sulphonated compound is desired, the molecular proportion of the sulphohating agent should be correspondingly increased so that the product which will be formed contains the desired number of sulphonate radicles in the aromatic nucleus.

To illustrate the present process, the following specific example is given:

64 parts by weight of anhydrous glycerine (99.5%) may be mixed with 526 parts by weight of fuming sulphuric acid (102.8%) at 30 C. and the resulting mixture stirred with 216 parts by weight of cocoanut oil, and`128 parts by weight of naphthalene at 80 C. or slightly less. 'I'he reaction will be completed withinapproximately 40 minutes', and the product may be neutralized with a 30 per cent aqueous solution of caustic soda at a temperature of around 40 C. to a pH. between 6.0 and 7.0. The neutralized product may then be dried in a spray tower to a white granular non-hygroscopic powder. Alternatively, the product may be dried on soapA drying rolls, mixed with perfume, llers, additional glycerine or other materials commonly added to soap and formed into bars or cakes.

Although the order of the process is preferably that described above and that which is shown by the drawings, it is possible to accomplish a sim ilar result by mixing the fatty oil or fatty acid, glycerine, or other polyhydric alcohol, aromatic material and sulphonating agent in any other order that may be desired. For example, fatty oil or fatty acid may be mixed with glycerine, and if desired reacted by heating with or without a catalyst, prior to the addition of the aromatic material and sulphonating agent. Alternatively, the sulphuric acid or other sulphonating agent may be reacted with the aromatic material prior to the addition of the glycerine and fatty oil or fatty acid. It has been found that, in general, it is not desirable to allow the sulphonating agent to act on the fatty oil prior'to the addition of the othervingredients, because the sulphonating agent tends to char the oil and thus darken the final product.

The drawings appended to this application show a system of apparatus for accomplishing the process as briefly outlined in the foregoing description. It is to be understood, however, that the process can be performed by other apparatus than that shown in these drawings and that various modifications in the process and apparatus, obvious to those skilled in the art, may be made.

Fig. 1 is a plan view of the apparatus adapted to perform the preferred process of this invention;

Fig. 2 is a side elevation view 0f a portion of the apparatus shown in Fig. 1;

Fig. 3 is a side elevation view of the spray dryer shown in Fig. l;

Fig. 4 is an end view of the apparatus shown in Fig. 2;

Figs. 5 and 6 are sectional views through the first and second mixers, respectively;

Figs. '1 and 8 are sectional views taken on lines 'I-I and 8-8 of Fig. 5, respectively;

Fig. 9 is a vertical'sectional view of the neutralizer; and

Fig. 10 is a horizontal sectional view of the neutralizer taken on the line IB-Il of Fig. 9.

The apparatus illustrated in the'drawings is a plant installation adapted for the continuous perfomance of the preferred process of this invention. In describing the operation of this apparatus, reference will be made to the raw materials as sulphuric acid, glycerine, cocoanut oil, naphthalene and caustic soda. It is to be understood, however, that these are used merely as preferred examples, and other equivalent materials or mixtures of the materials may be used instead. With this understood, it may be said generally that the apparatus operates first to mix the glycerine and sulphuric acid, then to react the mixture with cocoanut oil and naphthalene, and thereafter to neutralize the glycerine-acid-cocoanut oil-naphthalene product with caustic soda.

According to the preferred mode of applying the principles of this invention, substantially .anhydrous glycerine (around 99.5%) is supplied through pump II and pipe I2 to the first mixer I3. At the same time, fuming sulphuric acid' (around 102.8%) is supplied through a pump Il and pipe I5 to the same mixer. The pumps II and I4 and the pump for the fatty oil which will later be described are preferably geared together so that each will supply its respective reactant in exactly the desired proportion. Numerous types of proportioning devices are known, and any .one of these which is found suitable may be used in place of the pumps shown. As an additional precaution .to permit certainty with respect to the proportions of the reactants entering the mixer I3, volumeters or flow meters I6 and I I may be connected to the glycerine pipe I2 and the sulphuric acid pipe I5, respectively, near the point where the pipes connect to the mixer. Volumeters are calibrated vessels arranged to be filled, and the time of filling noted by a stop watch so as to calibrate or adjust the proportioning mechanism. 'I'hey drain back to the storage tanks after use.

As illustrated in Figs. 5, 7 and 8, the mixer I3 consists of a cylindrical shell Il closed at the bottom except for a drain opening I9. The top of the mixer is closed by a cover 20 upon which is mounted a driving motor 2| and suitable gearing 22 shown in Fig. 2. Through the top of the mixer a rotatably mounted vertical shaft 23 extends, and this shaft is connected to the motor 2I through the gearing so that it may be driven thereby. A series of radially extending mixing paddles 24, 25 and 26 are carried by shaft 23, and these paddles are constructed for movement within spaces arranged between hollow annular members 21 and 28 positioned within the cylinder. Cooling water is circulated through the hollow members by means of pipe connections as shown in Fig. 2.

As illustrated particularly in Pigs. 5 and 8, the paddles and the annular cooling members vary somewhat in form. The four upper cooling members 21 are somewhat smaller in diameter than the inside of the shell I3 and are'connected to their outer edges by cylindrical rings so that a portionoftheliquidinthemixermayiinwupf waidly from below the fourth member between the wall of the mixer and the perlpheries of these upper annular members and thus be mixed thoroughly with the fresh liquid as it enters the mixer. This action is aided by the construction of the paddles in the upper part of the mixer. Each of the three upper paddles 25 consists of a flat circular plate with four varies extending helically above it to throw the liquid outwardly and four helical vanes below the plate to draw the liquid inwardly and propel it downwardly through the. center opening in the underlying cooling element. The fiat circular portions of the paddles completely prevent anyof the liquid from passing directly downward along the shaft 23. All of the liquid is thus forced to travel out and around the edges of the circular portions of each of these three upper paddles. The fourth paddle from the upper end is an impeller 25 which must finally be passed by the liquid before it enters the lower part of the mixer. This impeller is of similar construction to the rst three paddles excepting that the four vanes above and the four vanes below the paddle are all arranged to throw the liquid upwardly and thus force a part of the liquid to return to the top of the mixer, andinducing a maximum mixingv action.

The two lower cooling members 28 are fit snugly to the shell by ring members and therefore all the liquid which passes these members must pass through the openings therein which surround the center shaft 23, and none can pass .upwardly around the outside. Paddles 26 lying below the fifth and sixth cooling member are but doubly radially projecting arms fastened to the shaft 28. A cross member 29 is provided at the bottom of the mixer, and this cross member carries a pin 3@ which enters an actual opening in the lower end of the shaft 23 to maintain the shaft in alinement. Cross member -29 is further provided with a pair of baiiles l3| which retard any rota.-

tion of the mixer and direct the liquid throug the drain opening it.

As will appear upon consideration of Figs. e and 5, the glycerine and sulphuric acid enter the mixers from pipes I2 and i5 and are /released into the mixer at the top and near its center.

They progress downwardly through the mixer as they become mixed and the mixture passes out through the drain opening i9. As the glycerine .and sulphuric acid are mixed, cooling water is circulated through the cooling members 2 and 2t to keep the temperature sumciently low'to prevent. darkening of the material. It has been` found that a temperature of approximately 30 C. is sufficiently low for this purpose, although lower temperatures may be used and slightly higher temperatures` may be permitted without lserious results.

Suitable pipes 532l are provided to supply water to the cooling members, the arrangement being such that the cooling water first enters the lower one of the four upper cooling members 2l from which it progresses upwardly to the top cooling member. It is thereafter conducted to the sixth or bottom cooling member 28 andv then to the fth cooling member and nally discharged. f

From the bottom of mixer'l the glycerine-A sulphuric acid mixture is conveyed by pipes 33 to a second mixer 34 at a point near the top. Cocoanut oil and naphthalene also enter this second mixer at a point near the top, being supplied by pump 35 and hopper Il through pipe 36 and dry powder feeder 'I2 and chute 13, respectively. The pump 35 is connected so as to supply a-quantity of fatty oil accurately proportioned to the amounts of glycerineand sulphuric 4acid supplied by pumps Il and I4, respectively.

The quantity of naphthalene added from hopper 'H is accurately proportioned to the amounts of fatty oil, glycerine and sulphuric acid entering the second mixer by means of an accurately controlled weighing system which regulates the dry powderl feeder l2. Numerous types of weighing systems are known and any one of these which is found suitable and which gives the desired degree of accuracy may be used. As with the glycerine first mixer are used as heating members in the y second mixer and hot water is passed therethrough to effect the heating. The hot water need not be circulated through the members in the order that the cooled water is circulated through the cooling members in the first mixture, but instead, the water may rst enter the top heating member and then vprogress downwardly through the next adjacent members in regular `order to the lowest member from which it is discharged.

Furthermore, there are but two of. the smaller sizedheat transfer members at the top of the second mixer, and only one of the paddles has its vanes arranged to throw outwardly above and draw inwardly below the nat circular portion. All of the vanes on the second paddle throwo'utwardly. The lower part of the second mixer includes only heat transfer members fitted closely A in the shell, and only double bladed radially extending mixing paddles are employed there- 1 between. Preferably the average temperature in this mixer is around 50 C. i

From the bottom of the 'second' mixer the glycerine-acid-cocoanut oil-naphthalene reaction product is conveyed too the top of the neutralizer t9 by transfer line 38. The neutralizar comprises a large cylindrical tank that' contains mixing and cooling equipment sunicient to thoroughly mix, at a controlled temperature, the glycerine-acid-cocoanut oil-naphthalene product with a neutralizing material which is preferably caustic soda. upper part of the mixer through a pipe 40 preferably as a solution of 30-50% concentration, being discharged into the neltralizer at about the same` point as the reaction product so that 'I'he caustic enters the the two materials .pass into immediate con-v iluence and the process of neutralization beginsl at once. Upon the admissionof the caustic and the reaction product into the neutralizer, the materials first pass'downwardly through .a cooling cylinder 4i and then upwardly between the outside of this cylinder and the wall of the neutralizer, which wall forms an additional cooling surface 42. Upon circulating to the upper end of the neutralizer, a part of the neutralized product is drawn off from the outside of the neutralizing cycle through pipe. 43 and conveyed to the drying equipment. The remainder is recycled with the incoming reaction product and caustic solution.

In order to thoroughly mix the caustic solution and the reaction product, agitation is provided in the form of a shaft 44 which extends downwardly through the top of the neutralizer and axially through the center of the inner cooling cylinder 4 I. This shaft is driven by an electric motor 45 through suitable gearing all mounted on the top of the neutralizer. Shaft 44 carries a series of impellers 46 within the inner cooling cylinder and a larger impeller 41 which is below the bottom of the inner cooling cylinder 4l for the circulation of the mixture. Appropriately shaped deflecting members 48 and 49 are provided to direct the mixture into the large impeller member 41 so as to obtain a maximum circulatory effect. 4I there is an axially extending cooling coil 50 which provides additional cooling surface, and a cooling water is fed through this coil into the bottom of the inner cooling cylinder and finally withdrawn from the top of that cylinder.

Between the inner and outer cooling cylinders 4l and 42 are a series of Scrapers that continually remove any of the product that solidiiies upon the cooling surface. As shown in Figs. 9 and 10, these scrapers comprise vertically extending straps 5l and 52 attached to the upright supporting members 55 and 56 and pressed against the inner and outer cooling cylinders respectively, by springs 53 and 54. The supporting members are in turn mounted upon'a spider 51 `car-v ried at the center of the bottom of the neutralizer tank upon a rotatable shaft 58 that extends through the bottom of the tank to suitable driving mechanism 59 and motor 60. The lower end of the agitator shaft 44 is' rotatably received in a cavity in the upper end of the shaft 58. Braces 6I and 62 may be used to join the scraper supporting members 55 and 56, respectively, so as to make a morerigid construction.

In order to control the amount of caustic added in accordance with the amount necessary to just neutralize the reaction product, a device is coni nected to the neutralizer for continuously measuring the hydrogen ion potential (pH) of the neutralized product, and this device controls an electrically operated valve 63 in the caustic line 40. The measuring device comprises a sampling pipe 64 through which a small amount of the mixed material is continually withdrawn from a point near the bottom of the inner cooling cylinder by the action of a small pump 65. From 4the pump the material is discharged to a baffle tank 66 in which are electrodes 61 connected to operate the electrically operated valve 63 through an electrometric titration device 68. Thus the amount of caustic supplied is controlled so as to always be just sufficient to neutralize the reaction product, and the neutralized material may be kept accurately at a pH of around 6.0 to 7.0, which has been found highly preferable. The material flowing through the baille tank is returned to the neutralizer by pipe 69.

After the product leaves the neutralizer, it is preferably conveyed by the pipe 43 to a spray drying device such as nshown in Fig.I 3 and described in Patent 1,652,900, patented to Dallas R. Lamont on December 13, 1927. Since this par- In the inner cooling cylinder of water which still remains with it is separated in a fine state of subdivision'linto a drying chamber 10 near the upper end. As it falls, it is contacted by a large volume of air forced down through the chamber by suitable pumping mechanism. By the time the product reaches the bottom of the chamber, it is dry and in the form of beads. These are drawn off ina current of air to the cyclone separator 14 where they are separated from the air in a form that is ready for packaging.

With the new product, there appears to be considerable advantage to spray drying, although, of course, the product may be dried in other'ways if desired. However, if the product is spray dried, it forms beautiful, exceptionally white beads that dissolve instantly in Water either hot or cold. While the apparatus described has been arranged to mix the glycerine and sulphuric acid prior to reacting them with the cocoanut oil and naphthalene, it is to be understood that this is only the preferred form and that other arrangements may be made. For example, glycerine and the cocoanut oil may be mixed in one mixer and the product sulphonated in the second mixer with a mixture of sulphuric acid 'and naphthalene, or cocoanut oil, glycerine and naphthalene may be mixed in the first mixer and sulphonated in the second mixer with sulphuric acid. Also, lime or other alkaline reagents may be used to effect the neutralization of the product and suitable means provided to settle, filter or centrifuge the product to remove the precipitate. Likewise, the electrometric titration apparatus may be changed to any desiredl form or even eliminated altogether.

As has been indicated above, the specific reacta nts mentioned as examples in the description of the process are not the only reactants that can be usedl according to this invention. For example, it is possible to use in place of cocoanut oil any other fatty oil of a generally similar nature, such as palm oil, olive oil, tallow, soy bean oil, fish oils, cottonseed oil, castor oil, peanut oil, rape oil, the fatty acids from any of these oi1s, naphthenic acid, abietic acid, or carboxylic acids formed by the oxidation of parailin hydrocarbons. Glycol, diethylene glycol or other polyglycols or polyglycerols may be used in place of glycerine. Similarly, chlorsulphonic acid or sulphur trioxide may be used in place of fuming sulphuric acid to perform the sulphonation and condensation. Other aromatic materials than naphthalene may also be used, as examples of which cresol, xylenol, benzol, benzyl naphthalene, toluol, pyrogallol, resorcinol, isobutylphenol and anthracene may be mentioned. Obviously, it will be necessary to modify the reaction conditions somewhat to compensate for the varying characteristics of the materials used, but the same general process of reaction will apply.

The final product which is formed by neutralizing with caustic soda. Will contain an appreciable amount of sodium sulphatelormed in the neutralization and this can either be removed or left in the final product according to the characteristics desired in that product. Sodium sulphate is not harmful to the effectivenessv of the product other than that it reduces the percentage of active ingredient in the inal product, and for. some purposes this'is desirable. To reinsoluble alcohol which will dissolve'the reacpounds unstable in the presence of alkalis, such tion product. or the process itself 'may be modified to avoid the formation of the sodium sulphate. If the product is neutralized with lime instead of with caustic soda, the resultant product contains calcium sulphate which is relatively insoluble and may be easily separated from the active ingredient. A 10% slurry of lime has been found entirely satisfactory for thispurpose. The triethanolamine salts of the reactant product-or the magnesium, ammonium, potassium or other salts may be made by simple base exchange ref actions withthe calcium salt of the reaction product. In performing such a reaction, a salt of the triethanolamine, ammonium, potassium, or magnesium is used, which salt will precipitate calcium from the solution and permit the desired base to replace it,J Such salts are the oxalates, carbonates, phosphates, or the like.

The nal product may be made intopowders,

lsalts such asGlauber salt and chalk; germicides such as phenol, hexylresorcinol and mercury chloride may also be incorporated with the material without injury either tothe effectiveness of the organic reaction product or the germicide. Perfumes and flavorings including organic comas isoeuginol, lanolin, and methylanthranilate; mildly acidic astringents such as aluminum chloride, zinc sulphate' and alum, deodorants, fatty acids, preservatives, starch, waxes, `rater and pigments and dyes of various kinds may all'be usedl in almost any desired combination or proportion.

We claim: I

l. A process for preparing a material suitable for use as a detergent that comprises reacting a material of the class consisting of fatty oils and fatty acids with a polyhydric alcohol, a sulphonating agent, and an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series, and thereafter 'neutralizing the reaction product by bringing 'the concentrated reaction product into conuence with a relatively concentrated solution of a neutralizing agent in the presence of a considerable quantity of already substantially neutralized material. i

f 2. A process for preparing a material suitable' for use as a detergent that comprises reacting a material of the class consisting of fatty oils and fatty acids with a polyhydric alcohol, a sulphonating agent, and an aromatic compound of the class consisting of compounds of the benzene,"

naphthalene and anthracene series, and thereafter neutralizing the reaction product by bring- Aing the concentrated reaction product into con-- fatty ons and 'fatty acids with a polyhydnc a1- cohol, a sulphonating agent and an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series at temperatures ranging from approximately to 80 C. and thereafter continuously neutralizing the reaction product 'into confluence with a concentrated solution of a neutralizing agent in the presence of an excess of already substantially neutralized product.

4. A process for preparing a material suitable for use as a detergent that comprises mixing a polyhydric alcohol and a sulphonating agent at a temperature of around 30 C. and condensing the mixture with an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series and a material of the class consisting offatty oils and fatty acids at a temperature of approximately 80 C. and thereafter neutralizing the nal product by bringing the concentrated reaction product into conuence` with a concentrated solution of a neutralizing agent in the presence of an excess of already substantially neutralized product at a temperature of around 40 C.

5. A process for preparinga material suitable for use as a detergent that comprises reacting a material of the class consisting of fatty oils and fatty acids with a polyhydric alcohol, a sulphonating agent, and an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series, and thereafter neutralizing the reaction product by bringing the concentrated reaction product into coniluence with a concentrated solution of a neutralizing agent in the presence of an excess of already substantially neutralized product and regulating the proportion of neutralizing agent to be added in accordance with the pH of the substantially neutralized product so as to maintain the pH thereof between 6.0 and '7.0.

6. A process for preparing a material suitable for use as -a detergent that comprises reacting approximately one molecular proportion of fatty oil, a slight excess over two molecular proportions of a polyhydric alcohol, an excess over three molecular proportions of a sulphonating agent and approximately three molecular proportionsv of an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series, and thereafter neutralizing the concentrated reaction product by bringing the same into conuence with a concentrated solutionof a neutralizing agent in the presence of an excess of already substantiallyneutralized product.

7. A process for preparing a material suitable for use as a detergent that comprises reacting approximately one molecular proportion of a fatty acid, a slight excess over one molecular proportion of a polyhydric alcohol, an excess o ver one molecular proportion of a sulphonating agent vand approximatelyone molecular proportion of an aromatic compound of the class consisting of compounds of the benzene, v`naphthalene and anthracene series and thereafter neutralizing the vconcentrated reaction product by bringing the same into confluence with a concentrated solution of a. neutralizing agent in the presence of an excess of already substantially neutralized product.

8. A process for preparing a material suitable for use as a detergent that comprises reacting approximately one molecularproportion of cocoanut'oil, around 5% more than two molecular 75 proportions of substantially anhydrous glycerine, an excess over threev molecular proportions of fuming sulphuric acid (approximately 102.8%), approximately three molecular proportions of naphthalene and neutralizing the concentrated reaction product with a concentrated solution of caustic soda (approximately to a pH of 6.0 to 7.0 in the presence of an excess of already substantially neutralized product.

9. A process for preparing a material suitable for use as a detergent that comprises reacting a material of the class consistingr of fatty oils and fatty acidslwith a polyhydric alcohol, a sulphonating agent, and an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series, said sulphonating agent being of the amount and concentration such that after the completion of the reaction the residual acid will possess a concentration of around 99% sulphuric acid or slightly above, and thereafter neutralizing the reaction product by bringing the reaction product into confluence with a concentrated solution of a neutralizing agent in the presence of an excess of already substantially neutralized product.

1,0. A process for preparing a material suitable for use as a detergent that comprises introducing a polyhydric alcohol and a sulphonating agent into a mixing zone, cooling and agitatlng the materials in the said zone, transferring the mixture of materials so formed to a second mixing zone, introducing an aromatic compound of the class consisting'of compounds of the benzene, naphthalene and anthracene series and a material of the class consisting of fattyA oils and fatty acids into said second mixing zone with said mixture, agitating and heating the material in said second mixing zone, transferring the procluct to a neutralizing zone, maintaining an excess of already substantially neutralized products in said 'neutralizing zone, bringing a concentrated solution of a neutralizing agent into confluence with the reaction product in said neu-A tralizing zone, regulating the amount of neutraling agent introduced so as to maintain the pH of the relatively large body at a pH of around 6.0 and '7.0.

11. A process for preparing a material for use as a detergent that comprises continuously reacting apprommately one molecular proportion of fatty oil, a slight excess over two molecular proportions of a polyhydric alcohol, an excess over three Jmolecular proportions of a sulphonating agent and approximately.three molecular proportions of an aromatic compound of the class consi sting of compounds of the benzene,.naphthalene and anthracene series, and thereafter continuously neutralizing the concentratedv reaction product by continuously bringing the reacv-'tlin product into confluence with the concentrated solution of a neutralizing agent in the presence of an excess of already `substantially neutralized A product.

12. A process for preparing a material suitable for use as a detergent that comprises continuously reacting approximately one molecular prov- I portion of a fatty acid, a slight excess over one molecular proportion of a polyhydric alcohol, anV

excess over one molecular proportion of a sulphonating agent and approximately one molecular proportion of an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series, and thereL after continuously neutralizing the concentrated reaction product by continuously bringing the reaction product into confluence with a concentrated solution of a neutralizing agent in the presence of an excess of already substantially neutralized product;

13. IA process for preparing a material suitable for use as a detergent that comprises reacting a material of the class consisting of fatty oils and fatty acids with glycerine, fuming. sulphuric acid and naphthalene and thereafter neutralizing the reaction product by bringing the concentrated reaction product into confluence with a relatively concentrated solution of a neutralizing agent in the presence of a considerable quantity of already substantially neutralized product.

14. A process for preparing a material suitable for use as a detergent that comprises reacting a material of the class consisting of fatty oils and fatty acids with glycerine, fuming sulphuric acid and cresol and thereafter neutralizing the reaction product by bringing the concentrated reaction product into confluence with a relatively concentrated solution of a neutralizing agent in the presence of a considerable quantity of already substantially neutralized product.

15.*A process for preparing a material suitable for use as a detergent that comprises reacting a material of the class consisting of fatty oils and fatty acids with glycerine, fuming sulphuric acid and an aromatic compound of 'the class consisting of compounds of the benzene, naphthalene and` anthraeene series and thereafter neutralizing the reaction product by bringing the concentrated reaction product into confluence with a relatively concentrated solution of a neutralizing agent in the presence of an excess of already substantially neutralized product.

16. A process for preparing a material suitable for use a detergent that comprises continuously introducing a polyhydric alcohol and a sulphonating agent into a mixing zone, continuously transferring the mixture of materials so formed to a second mixing zone, continuously introducing an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series and a material of the classA consisting of fatty oils and fatty acids into'said second' mixing zone with said mixture, agitating and heating the material in said second mixing zone, continuously transferring the product to a neutralizing zone, maintaining an excess of already substantially neutralized product in said neutralizing zone, continuously bringing a concentrated solution of a neutralizing agent into conuence with the reaction product in 'said neutralizing zone, regulating the amount of neutralizing agent introduced so as to maintain the pH of the relatively largeobody at a pH of around 6.0 to 7.0.

17. A process for preparing a material suitable for use as a detergent that comprises continuously reacting a material of the class consisting of fatty oils and fatty acids with a polyhydrlc alcohol, a sulphonating agent and an aromatic compound of the class consisting of compounds of the benzene, naphthalene and anthracene series, said sulphonating agent being of the amount and concentration such that after the completion of the reaction the residual acid possesses a concentration of around 99% sulphuricacid, or slightly above, and thereafter continuously neutralizing the reaction product by continuously bringing the reaction product into coniiuence with a concentrated solution of a neutralizing agent in the presence of an excess of already substantially neutralized product.

18. A process for preparing a material suitable with a relatively concentrated solution of a neu-- for use as a detergent that comprises reacting tralizing agent in the presence of a considerable a material of the class consisting of fatty oils quantity of already substantially neutralized and fatty acids with glycerine, fuming sulphuric product.

l acid and benzyl naphthalene and thereafter neu- EMIL E. DREGER. 5

tralizing the reaction products by bringing the JOHN ROSS. condensation reaction products into conuence 

